WO2010125717A1 - 化学センサ - Google Patents

化学センサ Download PDF

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Publication number
WO2010125717A1
WO2010125717A1 PCT/JP2010/000748 JP2010000748W WO2010125717A1 WO 2010125717 A1 WO2010125717 A1 WO 2010125717A1 JP 2010000748 W JP2010000748 W JP 2010000748W WO 2010125717 A1 WO2010125717 A1 WO 2010125717A1
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WO
WIPO (PCT)
Prior art keywords
sensor
sample
electrode
tft
chemical sensor
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PCT/JP2010/000748
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English (en)
French (fr)
Japanese (ja)
Inventor
柴田佳典
足立昌浩
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シャープ株式会社
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Priority to CN2010800060820A priority Critical patent/CN102301227A/zh
Priority to US13/147,798 priority patent/US20110291673A1/en
Publication of WO2010125717A1 publication Critical patent/WO2010125717A1/ja

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403—Cells and electrode assemblies
    • G01N27/414—Ion-sensitive or chemical field-effect transistors, i.e. ISFETS or CHEMFETS
    • G01N27/4145—Ion-sensitive or chemical field-effect transistors, i.e. ISFETS or CHEMFETS specially adapted for biomolecules, e.g. gate electrode with immobilised receptors
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403—Cells and electrode assemblies
    • G01N27/414—Ion-sensitive or chemical field-effect transistors, i.e. ISFETS or CHEMFETS
    • G01N27/4148—Integrated circuits therefor, e.g. fabricated by CMOS processing

Definitions

  • the present invention relates to a chemical sensor, and more particularly to a chemical sensor using a thin film transistor.
  • FIG. 6 is a cross-sectional view showing the configuration of a conventional ISFET.
  • the ISFET 100 has a structure in which the gate electrode is removed from a normal MOSFET and the region of the channel 104 is covered with an ion sensitive film 106.
  • specific ions to be detected in the sample solution 108 selectively react with the ion sensitive film 106.
  • the surface potential of the gate portion changes, and the drain current changes.
  • the biosensor ISFET100 and detects the change in the drain current I d.
  • Patent Documents 1 and 2 describe a biosensor using a thin film device such as a polysilicon TFT as an ISFET. Further, an ISFET array in which a plurality of ISFETs are two-dimensionally arranged is also known, and Patent Document 3 describes an ISFET array in which the influence of noise due to a switching operation is reduced.
  • the ISFET uses an ion sensitive membrane to detect specific ions. Therefore, it is necessary to use different ion sensitive membranes depending on ions to be detected. Therefore, it is disadvantageous in terms of cost in order to meet the need to use various sample solutions.
  • the present invention has been made in view of the above problems, and an object thereof is to provide a chemical sensor that does not require an ion-sensitive film.
  • a chemical sensor for detecting an object in a sample, and includes a gate electrode, a gate insulating layer, a semiconductor layer, a source electrode, and a drain electrode on a substrate.
  • a channel region is formed in the semiconductor layer in the opening between the source electrode and the drain electrode, and further includes a current extraction unit that extracts a leakage current generated in the channel region. It is the composition which is.
  • the chemical sensor includes the thin film transistor having the gate electrode, the gate insulating layer, the semiconductor layer, the source electrode, and the drain electrode on the substrate, and the current extraction unit that extracts the leakage current.
  • a thin film transistor an opening is formed between a source electrode and a drain electrode, and a channel region is formed in a semiconductor layer in the opening. Therefore, the object in the sample can approach the channel region from the opening.
  • the leakage current can change in the channel region due to the back channel effect.
  • the current extraction unit can detect a change in the leakage current by extracting the leakage current. Therefore, according to the chemical sensor of the present invention, the presence or absence of an object in the sample can be detected as a change in the intensity of the leakage current. For this reason, an object can be detected without providing an ion sensitive film like a conventional ISFET.
  • the back channel effect is a phenomenon in which holes or electrons are induced in the back channel by external ions or the like.
  • the back channel is a path through which a leak current flows on the surface of the semiconductor layer at the opening between the source electrode and the drain electrode.
  • a detection method for detecting an object in a sample, and includes a gate electrode, a gate insulating layer, a semiconductor layer, a source electrode, and a drain electrode on a substrate.
  • a thin film transistor in which a channel region is formed in the semiconductor layer in an opening between the source electrode and the drain electrode, and a current extraction unit that extracts a leakage current generated in the channel region.
  • a step of bringing the sample into contact with a chemical sensor, a step of taking out the leakage current generated when the sample is brought into contact with a current extraction unit, and a change in intensity of the taken out leakage current And a step of detecting the object.
  • the detection of the target is performed by taking out the leak current generated by the presence or absence of the target in the sample and using the change in the leak current. That is, the presence / absence of an object in the sample can be detected as a change in the intensity of the leakage current. Therefore, the object in the sample can be detected without using the ion sensitive membrane.
  • the chemical sensor according to the present invention includes a thin film transistor having a semiconductor layer and a current extraction unit that extracts a leakage current generated in a channel region of the semiconductor layer, and an opening between the source electrode and the drain electrode. Since the channel region is formed in the portion, the presence / absence of the object in the sample can be detected as a change in the intensity of the leakage current.
  • FIG. 4C is a characteristic graph of the relationship between the gate voltage and the drain current in FIG. 4A
  • FIG. 4D is the graph in FIG. It is a characteristic graph of the relationship between gate voltage and drain current.
  • It is a double view which shows the external appearance of one Embodiment in the chemical sensor of this invention.
  • It is a schematic sectional drawing of the conventional ISFET sensor. It is a top view which shows the external appearance of another embodiment in the chemical sensor of this invention.
  • FIG. 1 is a block diagram showing the configuration of the biosensor of the present invention.
  • the biosensor 1 includes a sensor array 2, a sensor array driving circuit 22 and a scanning signal line driving circuit 23 that send signals to the sensor array 2, and a sensor signal amplification and extraction circuit ( (Current extraction part) 24 is comprised.
  • the sensor array 2 includes a plurality of sensor TFTs (thin film transistors) 7.
  • FIG. 2 is a cross-sectional view showing a schematic configuration of the sensor TFT 7.
  • the sensor TFT 7 includes a glass substrate (substrate) 8, a base coat film 9, a gate electrode 10, a gate oxide film (gate insulating layer) 11, a silicon layer (semiconductor layer) 12, an n + layer 13, and a source electrode. 14, a drain electrode 15, a passivation film 16 and a shield film 17.
  • a channel region 18 is formed in an opening between the source electrode 14 and the drain electrode 15 in the silicon layer 12.
  • a TFT conventionally used for driving a liquid crystal panel can be used.
  • the back channel in the present embodiment refers to a path through which a leakage current flows on the silicon layer 12 side at the interface between the silicon layer 12 and the passivation film 16 in the opening between the source electrode 14 and the drain electrode 15.
  • a region where a back channel is formed is referred to as a back channel region.
  • the shield film 17 plays a role of electrically shielding the sample base material from the source electrode 14 and the drain electrode 15 when the sample base material (target object) to be detected is charged.
  • an oxide film containing conductive particles uniformly may be used, or an oxide film having a very large film thickness may be used.
  • the passivation film 16 is not particularly limited as long as it is not affected by the sample solution used for detection.
  • a SiNx film can be used as the passivation film 16.
  • the sample base material in the sample can approach the channel region 18.
  • the biosensor 1 detects a change in the intensity of leak current that may occur when the sample substrate approaches the channel region 18. Therefore, the presence or absence of the sample base material can be detected by detecting the change in the leakage current.
  • the leak current resulting from the presence or absence of the sample base material is generated by the following process. For example, when the sample substrate contained in the sample solution is positively charged as a whole, the entire passivation film 16 is polarized with the sample solution side negative and the silicon layer 12 side positive.
  • the passivation film 16 Due to the polarization of the passivation film 16, electrons are attracted to the vicinity of the interface of the silicon layer 12 with the passivation film 16, thereby forming a channel (back channel). Since a back channel is formed in the silicon layer 12, a leakage current is generated.
  • the passivation film 16 preferably contains impurity ions.
  • the negative impurity ions in the passivation film 16 are attracted to the sample solution side due to the presence of the positively charged sample base material, and the sample solution and It is distributed at the interface with the passivation film 16.
  • the polarization in the passivation film 16 becomes larger than that in the case where the passivation film does not contain impurities, and a larger leakage current can be generated. That is, the biosensor 1 does not require an ion sensitive film used in a conventional ISFET sensor.
  • size of drain current is amplified by making the gate oxide film 11 thin, and it can improve a measurement sensitivity by this.
  • the glass substrate 8 is used as the substrate of the sensor TFT 7, but a substrate formed of a polymer material such as polycarbonate may be used.
  • a substrate formed of a polymer material such as polycarbonate
  • the gate electrode 10, the gate oxide film 11, the silicon layer 12, the n + layer 13, the source electrode 14, the drain electrode 15, and the passivation film 16 may be formed of an organic material.
  • the gate electrode 10, the source electrode 14, and the drain electrode 15 can be formed using an organic conductor such as polyacetylene.
  • the gate oxide film 11 and the passivation film 16 can be formed using an organic insulator such as polyimide.
  • the silicon layer 12 and the n + layer 13 can be formed using an organic semiconductor such as pentacene.
  • the sensor array 2 includes n gate voltage signal lines G 1 to G n , m sensor reset signal lines RS 1 to RS m , and m sensor read signal lines RW 1 to RW m. , And (m ⁇ n) sensor circuits 28.
  • the sensor array 2 further includes n extraction signal lines (current extraction units) PAS 1 to PAS n .
  • m and n are integers of 1 or more.
  • the gate voltage signal lines G 1 to G n are arranged in parallel to each other.
  • the sensor reset signal lines RS 1 to RS m and the sensor readout signal lines RW 1 to RW m are arranged in parallel to each other so as to be orthogonal to the gate voltage signal lines G 1 to G n .
  • the sensor circuit 28 includes a sensor TFT 7, a preamplifier TFT 25, and a capacitor 26, and is arranged on the sensor array 2 in an array.
  • the gate terminal of the sensor TFT 7 is connected to a gate voltage signal line G i (i is an integer of 1 to n).
  • a source terminal of the sensor TFT 7 is connected to a sensor reset signal line RS j (j is an integer of 1 to m).
  • the drain terminal of the sensor TFT 7 is connected to one electrode of the capacitor 26.
  • the other electrode of the capacitor 26 is connected to the sensor readout signal line RW j .
  • the gate terminal of the preamplifier TFT 25 is connected to the drain terminal of the sensor TFT 7 at the contact P.
  • a power supply voltage V DD is applied to the source terminal of the preamplifier TFT 25.
  • the drain terminal of the preamplifier TFT25 is connected to the signal line PAS i extraction.
  • the scanning signal line driving circuit 23 is a circuit that transmits gate voltage signals G 1 to G n for controlling on / off of the sensor TFT 7 to each sensor TFT 7 on the sensor array 2.
  • the sensor array driving circuit 22 is a circuit that transmits sensor read signals RW 1 to RW m and sensor reset signals RS 1 to RS m to each sensor TFT 7 on the sensor array 2.
  • the gate voltage signals G 1 to G n can be controlled by the timing control signal C 1 from the host CPU 21, and the sensor read signals RW 1 to RW m and the sensor reset signals RS 1 to RS m are controlled by the timing control signal from the host CPU 21. It can be controlled by a signal C 2.
  • the sensor signal amplification / extraction circuit 24 extracts the signals PAS 1 to PAS n of the sensor TFT 7 from the sensor array 2, amplifies the signals, and transmits them to the host CPU 21.
  • the operation in the sensor circuit 28 in the detection method for detecting the sample base material in the sample using the biosensor 1 will be described.
  • this detection method first, the sample is brought into contact with the vicinity of the channel region 18 of the sensor TFT 7. At this time, due to the back channel effect due to the presence or absence of the sample base material in the sample, the leakage current intensity changes in the back channel region of the TFT 7 and the drain current changes.
  • the sample base material in the sample is detected by taking out the leak current / drain current and examining the change in the leak current.
  • FIG. 3 is a diagram showing one of the sensor circuits 28 of the sensor array 2 extracted.
  • a predetermined voltage is applied to the sensor readout line RW i and the sensor reset line RS i , and a power supply voltage V DD is applied to the source terminal of the preamplifier TFT 25.
  • V DD power supply voltage
  • a sample substrate is present in the vicinity of the channel region 18 of the sensor TFT 7
  • a back channel 27 is formed in the sensor TFT 7. Due to the back channel effect, the leakage current in the back channel 27 increases, and the drain current of the sensor TFT 7 increases.
  • the voltage at the contact P decreases by the amount of the flowing current.
  • a high voltage is applied to the sensor readout line RW i to increase the voltage at the contact P
  • the gate voltage of the preamplifier TFT 25 is set to be equal to or higher than a threshold value
  • the power supply voltage V DD is applied to the source terminal side of the preamplifier TFT 25.
  • the power supply voltage V DD is applied, the voltage at the contact P is amplified by the preamplifier TFT 25, and the amplified voltage is output to the drain terminal side of the preamplifier TFT 25.
  • the sensor signal amplifying / extracting circuit 24 transmits this detection result to the host CPU 21, and the host CPU 21 performs arithmetic processing.
  • the host CPU 21 detects the sample base material from the change in the leak current by a calculation process.
  • FIG. 4 is a diagram showing the difference in drain current caused by the presence or absence of the sample base material 19.
  • FIG. 4A shows the sensor TFT 7 when the sample base material 19 to be detected does not exist in the surroundings
  • FIG. 4C shows characteristics representing the relationship between the gate voltage and the drain current at that time. It is a graph.
  • FIG. 4B shows the sensor TFT 7 when the sample base material 19 exists in the surroundings
  • FIG. 4D is a characteristic graph showing the relationship between the gate voltage and the drain current at this time. is there.
  • the drain current for the same gate voltage increases as compared to FIG. 4C showing the case where the sample base material 19 does not exist. That is, an increase in leak current can be detected from an increase in drain current, whereby the presence of the sample substrate 19 can be detected. Further, it differs depending on the amount of leakage current, the shape of the drain current-gate voltage characteristic graph, or the use of the sensor array 2 which is the array-shaped biosensor 1 shown in FIG. It is possible to identify the type of sample base material 19.
  • FIG. 5 is a schematic two-view diagram of an embodiment of the biosensor 1, showing a top view and a cross-sectional view.
  • the biosensor 1 has a matrix structure that is partitioned into a plurality of ridge-like structures 3 by partitioning a base body 4, and forms a sensor array 2 that is in the form of an array.
  • a sensor TFT 7 having a comb source electrode 14 and a drain electrode 15 is arranged on the bottom surface of each bowl-like structure 3.
  • a sample solution 5 is added to each bowl-like structure 3 and detection is performed by the sensor TFT 7. Note that different sample solutions can be added to each bowl-like structure 3. Therefore, it is possible to perform detection work on a plurality of different samples at the same time. Further, by using the array sensor 2 as described above, different types of sample base materials 19 can be identified.
  • FIG. 7 is a plan view schematically showing the sensor array 2.
  • the sensor array is composed of four sections each having a sensor TFT 7.
  • any one of the substances A to D is put in each of the sections a to d.
  • chemical reaction conditions for the substances X and Y in the substances A to D are determined as shown in Table 1.
  • each substance is ionized by this chemical reaction, and a leak current is generated in the sensor TFT 7 due to the presence of the generated ions.
  • the method for identifying the type of sample base material is not limited to using the sensor array 2.
  • the substance A becomes a divalent ion by the reaction with the substance X and the substance B becomes a monovalent ion by the reaction with the substance X
  • the ion concentration of the ions generated by the reaction becomes different.
  • the amount of carriers induced in the back channel is different, and the magnitude of the leak current generated is different. Therefore, even if the biosensor 1 is not in the array form, it is possible to identify the type of the sample base material by measuring the magnitude of the leakage current.
  • the measurement object of the biosensor 1 according to the present invention is not particularly limited. For example, it is possible to detect ions in the sample solution. Further, as described above, it is also possible to detect ions generated by a chemical reaction between a substance contained in a sample and another substance. When the ion concentration is different, the amount of polarization charge in the passivation film 16 is also different. As a result, since the amount of carriers induced in the back channel of the silicon layer 12 is different, the magnitude of the leakage current is also different. That is, the back channel effect varies depending on the difference in ion concentration in the sample solution, and the magnitude of the leakage current changes accordingly.
  • a DNA chip that detects the presence or absence of target DNA by the presence or absence of hybridization as follows.
  • the complementary strand of the target DNA is bonded to the passivation film 16 or the shield film 17 between or near the source electrode 14 and the drain electrode 15 and ionized.
  • ionization of the complementary strand is eliminated.
  • a change occurs in the ionization state in the vicinity of the back channel region depending on the presence or absence of hybridization, resulting in a change in leakage current.
  • binding of complementary strand DNA to the passivation film 16 and the like, ionization, and the like may be performed by a conventionally known method.
  • the sample substrate 19 is detected by utilizing the back channel effect of the TFT. Therefore, an ion sensitive film is not necessary, and the sensor TFT 7 can be manufactured in a conventional TFT process used for manufacturing a liquid crystal panel. Since the materials and processes used for manufacturing generally follow the conventional TFT manufacturing process, the same production amount and cost as those of the TFT portion of the conventional liquid crystal panel can be secured.
  • the gate voltage can be actively applied to the sensor TFT 7 by the gate electrode 10. As a result, the drain current can be controlled.
  • the substrate is preferably made of a polymer material.
  • the chemical sensor can be further reduced in weight.
  • At least one of the gate electrode, the gate insulating layer, the semiconductor layer, the source electrode, and the drain electrode is formed of an organic material.
  • the chemical sensor can be further reduced in weight.
  • the chemical sensor can be made flexible by forming all of it with an organic material.
  • the plurality of thin film transistors are arranged in an array, and each of the plurality of thin film transistors is partitioned by a partition.
  • each of a plurality of different samples can be provided to each thin film transistor. Therefore, it is possible to perform detection work on a plurality of samples at the same time.
  • the present invention can be used in the medical field for analyzing biological samples and other chemical substances.
  • Biosensor (chemical sensor) 2 Sensor array 7 Sensor TFT (Thin Film Transistor) 8 Glass substrate (substrate) 9 Base coat film 10 Gate electrode 11 Gate oxide film (gate insulating layer) 12 Silicon layer (semiconductor layer) 13 n + layer 14 Source electrode 15 Drain electrode 16 Passivation film 17 Shielding film 18 Channel region 19 Sample base material (object) 22 sensor array driving circuit 23 scanning signal line driving circuit 24 sensor signal amplification / extraction circuit (current extraction unit) 25 Preamplifier TFT 27 Back channel 28 Sensor circuit 100 ISFET 101 Substrate 102 Drain electrode 103 Source electrode 104 Channel 105 Protective insulating film 106 Ion sensitive film 107 Reference electrode 108 Sample solution

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PCT/JP2010/000748 2009-04-27 2010-02-08 化学センサ WO2010125717A1 (ja)

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Application Number Priority Date Filing Date Title
CN2010800060820A CN102301227A (zh) 2009-04-27 2010-02-08 化学传感器
US13/147,798 US20110291673A1 (en) 2009-04-27 2010-02-08 Chemical sensor

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JP2009-108442 2009-04-27
JP2009108442 2009-04-27

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